<P> The occurrence of silver in galena, chalcopyrite, sphalerite, and pyrite as well as tailings from Cart Lake, Cobalt Ontario were investigated to compare with the undetectable ( <10^-11 g/g) Ag found in runoff water from the Cobalt area. </p> <p> Silver was detected at very low levels: 0.012 wt% ± 0.009 wt%, 0.015 wt% ± 0.01 wt%, and 0.0062 wt% ±0.02 wt% for pyrite, galena and chalcopyrite, respectively. </p> <p> Attempts to characterize the mineralogical associations of silver were not successful. The silver sequence of pyrite> galena> chalcopyrite is contrary to results from other studies. This may be due to the maximum thermal stabilities of the minerals in relation to the ions available for replacement. </p> / Thesis / Bachelor of Science (BSc)

A gradual depletion of high-grade ores, coupled with the growing demand for mineral commodities across the world has culminated in the increased exploitation of lean-grade ores with complex mineralogy. The mineral processing industry commonly uses an extensive range of inorganic, naturally derived or synthetic organic reagents in the separation of valuable minerals from the ore. Froth flotation is a commonly used separation technique to float or depress different sulfide minerals from the ore, based on their surface properties. In recent times, biological processes have been attracting attention in mineral processing and metal recovery operations due to a number of factors, especially lower operating costs, lesser energy consumption and their environment friendly nature. The use of microorganisms and their direct derivatives in mineral processing, hydrometallurgy and in the bioremediation of mineral industry discharges has led to the emerging area of “Mineral Bioprocessing”. In this study, a family of four microorganisms belonging to the Bacillus species, viz., Paenibacillus polymyxa, Bacillus circulans, Bacillus megaterium and Bacillus subtilis was used to ascertain the selective floatability of sphalerite from a sphalerite-galena mineral mixture. These bacteria are Gram positive, mesophilic, neutrophilic, aerobic and spore forming. The major objectives of the investigation include: a) Identification and characterization of bioreagents derived from Bacillus species for the flotation of sphalerite from a sphalerite-galena mixture b) Optimization of the flotation process for the enhanced recovery of sphalerite using specific bioreagent combinations c) Modes and mechanisms of bacterial adaptation to minerals and their consequent effects on the flotation of sphalerite and galena d) Elucidation of the mechanisms of microbe-mineral interactions and the role of extracellular secretions in sphalerite flotation column and their N-terminal residues were identified using Edmann N-terminal sequencing. Additionally, sequences of several internal peptides from both the proteins were determined using Tandem Mass Spectrometric techniques. A database search revealed that the sequences of these peptides are unique and have not been reported earlier. It was established that the bacterial cells give high flotation recovery of sphalerite under buffered conditions and that it took place only in the presence of anionic buffers. Additionally, the viability of the bacterial cells was not required for the flotation of minerals. A major finding of this study was that other than extracellular DNA (eDNA), none of the other bacterial surface components like teichoic acids, surface proteins, polysaccharides played a positive role in the flotation process. Nucleic acids, more particularly single stranded DNA (ssDNA), facilitated sphalerite flotation relative to double stranded DNA (dsDNA). A probable mechanism of ssDNA -mediated selective flotation of sphalerite has been presented. A negative role for non-DNA surface components was also observed. This led to the realization of the need for an optimum ratio of DNA to non-DNA components in the selective flotation of sphalerite from a sphalerite-galena mixture. It was found that the surface physiochemical properties of the mineral adapted bacteria differed significantly from that of the unadapted bacteria. Adaptation enhanced the flotation recoveries of the corresponding mineral vis-à-vis the unadapted bacteria. Sphalerite adapted bacteria secreted more extracellular proteins while the galena adapted bacteria secreted more polysaccharides compared to the unadapted bacteria. Sphalerite adapted bacteria selectively floats more sphalerite from the mineral mixture than the galena adapted as well as the unadapted bacteria. It was evident from the electrokinetic studies that the surface charge of the chosen sulfide mineral adapted bacteria was less negative relative to the unadapted bacteria. This phenomenon was observed with all the four bacterial species used in this study. A noteworthy finding was that the bacteria especially B.circulans induce a change in morphology from rod to sphere as a strategy during adaptation to a toxic mineral such as galena. This phenomenon has been shown to involve changes in crucial cell wall components as well as changes in the levels of expression of bacterial cytoskeleton elements involved in the maintenance of the rod shape. This aspect of the study involved the partial sequencing of the B.circulans homolog of the key cytoskeleton gene, mreB (B gene in murien cluster e), using the Polymerase Chain Reaction (PCR) followed by DNA sequencing. A Genbank search indicated that this is the first report of the sequence of B.circulans mreB gene. This was followed by measuring the hypothesized downward changes in the levels of expression of the mreB gene by Reverse Transcriptase Polymerase Chain Reaction (RT-PCR). The possible mechanisms of the adaptive morphological changes and of the interaction of the chosen sulfide minerals with the family of microorganisms studied have been discussed with respect to their bioflotation efficiency.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 239-244).

This thesis deals with the isotopic composition of lead and 210 lead in recent galena from burning heaps after coal mining in the Lower Silesian basin. The studied sites were heaps in Radvanice, Markoušovice and Rybníček, where samples of galena, coal and burnt rocks were available. For the determination of the isotopic composition was used mass spectrometry with inductively coupled plasma (ICP - MS). Mass 210 Pb activity in galena was measured in a gamma - spectrometer Silar and the effect of radioactivity on galena crystal lattice was determined by the modified Williamson - Hall graph which was made from taken X-ray diffraction data. The values of isotope ratios in galena ranged for 207 Pb/206 Pb = 0,8402 to 0,8435 and for 208 Pb/206 Pb = 2,0663 to 2,0836. The average values of the coal were measured for 207 Pb/206 Pb = 0,8312 and 208 Pb/206 Pb = 2,0421. On the basis of these isotope ratios was found out that during the burning of coal and subsequent galena crystallization from hot gases there is no isotopic fractionation. Mass 210 Pb activity in galena ranged from 135 ± 9 Bq/g to 714 ± 22 Bq/g. Radioactivity of galena causes the developement of micro-deformation in the crystal structure. This micro-deformation is demonstrated by increased micro-strain in the crystal lattice. The level of this...

The Silver Hart property is a high grade silver-lead-zinc deposit consisting of polymetallic vein style, manto (carbonate replacement) style, and skarn type mineralization. Host rock consists of calcareous and non-calcareous sediments of the Cassiar Platform, mainly biotite schists, limestone units, and the monzogranite unit of the Cassiar Batholith. Bulk geochemistry shows that silver concentrations are closely related to copper and antimony values, suggesting freibergite, a silver-rich endmember of tetrahedrite, is the dominant silver mineral. EPMA (microprobe) analyses identified 6 silver minerals present; silver-bearing anglesite, freibergite, diaphorite, stephanite, pyrargyrite, and silver substitution in galena. Sulfur isotope analyses of galena gave an average δ34S of 6.9‰ vs VCDT, indicating a mixed mineralizing fluid source. Metal zoning patterns indicates that there is a thermal gradient across the main vein from hottest in the south-west, above the monzogranite intrusion, to coolest in the north-east. Microprobe analyses of freibergite indicates initial ore-forming fluid temperatures were between 250°C - 350°C, with subsequent cooler mineralization fluids of 170°C - 200°C.

The acidic, non-oxidative dissolution of galena nanocrystals has been studied using both microscopic and wet-chemical methods. The effects of particle size, shape, aggregation state, and grain proximity on dissolution rates were investigated. Nearly monodisperse galena nanocrystals with an average diameter of 14.4 nm and a truncated cubic shape were synthesized. In the dissolution experiments of dispersed nanocrystals, galena nanocrystals attached on the surface of a TEM grid were exposed to deoxygenated HCl solutions (pH 3) at 25 °C. Capping groups on nanocrystals were removed via a washing process, and chemistry of nanocrystals was examined using X-ray photoelectron spectroscopy (XPS). The evolution of the size and shape of the pre- and post-dissolution nanocrystals were studied using transmission electron microscopy (TEM), and the dissolution rate was calculated directly according to the size shrinking of galena nanocrystals. To assess the size effect, galena microcrystals (~ 3 μm) were synthesized and dissolved under similar conditions to the dispersed nanocrystals. The results showed that the nanocrystals dissolved at a surface area normalized rate of one order of magnitude faster than the microcrystals. In addition, dissolution rate is orientationdependent on a single nanocrystal. High-resolution TEM (HRTEM) images indicated the {111} and {110} faces dissolve faster than {100} faces on galena nanocrystals, rationalized by the average coordination number of ions on each of these faces. To assess the aggregation effect, dissolution experiments of aggregated galena nanocrystals were conducted using a wet-chemical method, and the results were compared with the rates of microcrystals and dispersed nanocrystals. These experiments showed that the rate of aggregated nanocrystals is in the same order of magnitude as the rate of microcrystals, but one order of magnitude smaller than that of dispersed nanocrystals. Finally, the effect of the close proximity between nanocrystals on dissolution was observed by HRTEM. Dissolution was greatly inhibited on nanocrystal surfaces that were closely adjacent (1-2nm, or less) to other nanocrystals, which is probably relevant to the slow dissolution of aggregated nanocrystals. The dissolution phenomena of galena nanocrystals observed in this study is likely important for understanding the environmental fate and behavior of nanoparticles in aquatic systems. / Ph. D.

Scanning tunneling microscopy (STM) images and scanning tunneling spectroscopy (STS) spectra of galena (PbS) and hematite (a-Fe203) were calculated using ab-initio methods in order to interpret experimental images and spectra that were taken in previous studies. These calculations have helped to understand which states of the mineral surfaces were imaged depending on the bias voltage and tip-sample separation. The computational results also gave insight in electron transfer processes that take place during surface adsorption/oxidation/reduction processes. In this context, different oxidation (using O₂ and ferric iron as oxidants) and gold adsorption/reduction mechanisms on galena were evaluated at an atomic level. On hematite, the main emphasis was determining the differences in the local electronic structure of specific sites above the surface and the electronic structure of the bulk. Hereby, step sites turned out to have an increased local density of states at certain electron binding energies that are absent on flat surfaces. states can explain the highly increased reactivity of step sites as compared to terraces. X-ray photoelectron spectra (XPS) were calculated to compare the photoelectron peaks of the calculated specific surface structures (that do not have a bulk equivalent) with experimentally obtained XPS spectra. Most of the calculated peak chemical shifts coincided with those that were found in experiments and that were previously interpreted in terms of known bulk structures. Therefore, it can be inferred that the conventional way of interpreting XPS spectra might be incomplete if specific surface structures are neglected. In order to understand step velocities on a gypsum (010) surface, step energies of different step directions were calculated using an ab-initio approach. An approximately linear relationship was found between the calculated step energies and the experimentally determined step velocities. / Ph. D.

The major objective of this work was to investigate the initial oxidation behavior of pyrite in order to better understand how mine wastes containing pyrite generate acid water. It was found that a unique potential exists at which a fresh surface of pyrite undergoes neither oxidation nor reduction. This potential is pH dependent and is referred to as the "stable" potential. The stable potential was found to be 0 V at pH 4.6 and -0.3 V at pH 9.2. Fresh, unoxidized pyrite surfaces were obtained by fracturing under the electrolyte while holding at the stable potentials. The initial oxidation behavior of pure pyrite was investigated using cyclic voltammetry technique by beginning potential sweeps from the stable potential and sweeping in the positive-going or negative-going direction. The effects of semiconducting properties of pyrite on its electrochemical behavior were studied by photocurrent measurement. The results indicate that pyrite samples from Peru and Spain are all highly n-type. A spontaneous depletion layer is formed on the fresh surfaces of n-type pyrite. The depletion layer is attributed to an intrinsic, acceptor-like surface state. Charge storage in this surface state pins the band edge over a wide potential range, accounting for the metallic-like electrochemical behavior that has been reported for pyrite. Electrochemical and photocurrent measurements were also conducted on galena for comparison with pyrite. The results indicate that galena samples from the same cluster have varying semiconducting properties, ranging from nearly intrinsic to highly n-type. Abrasion introduces defects in the surface of pyrite and galena, which strongly decrease the magnitude of photocurrent. / Master of Science

Hydrophobic interaction plays an important role in biology, daily lives, and a variety of industrial processes such as flotation. While the mechanisms of hydrophobic interactions at molecular scale, as in self-assembly and micellization, is relatively well understood, the mechanisms of macroscopic hydrophobic interactions have been controversial. It is, therefore, the objective of the present work to study the mechanisms of interactions between macroscopic hydrophobic surfaces in H-bonding liquids, including water, ethanol, and water-ethanol mixtures. The first part of the present study involves the measurement of the hydrophobic forces in the thin liquid films (TLFs) confined between two identical hydrophobic surfaces of contact angle 95.3o using an atomic force microscope (AFM). The measurements are conducted in pure water, pure ethanol, and ethanol-water mixtures of varying mole fractions. The results show that strong attractive forces, not considered in the classical DLVO theory, are present in the colloid films formed with all of the H-bonding liquids tested. When an H-bonding liquid is confined between two hydrophobic surfaces, the vicinal liquid molecules form clusters in the TLFs and give rise to an attractive force. The cluster formation is a way to minimize free energy for the molecules denied of H-bonding with the substrates. Thus, solvophobic forces are the result of the antipathy between the CH2- and CH3-coated surface and H-bonding liquid confined in the film. A thermodynamic analysis of the solvophobic forces measured at different temperatures support this mechanism, in which solvophobic interactions entail decreases in the excess film enthalpy and entropy. The former represents the energy gained by building clusters, while the latter represents loss of entropy due to structure building. Thus, hydrophobic interaction may be a subset of solvophobic interaction. The solvophobic forces are strongest in pure water and pure ethanol, and decrease when one is added to the other. Adding a very small amount of ethanol to water sharply reduced the solvophobic force due to the adsorption of the former with an inverse orientation. An exposure of the OH-group toward the aqueous phase decreases the antipathy between the surface and H-bonding liquid and hence causes the hydrophobic (or solvophobic) forces to decrease. The second part of the study involves the measurement of the hydrophobic forces in the wetting films of water using the force apparatus for deformable surfaces (FADS). This new instrument recently developed at Virginia Tech is designed to monitor the deformation of bubbles to determine the surface forces in wetting films. In effect, an air bubble is used a force sensor. The measurements have been conducted with gold, chalcopyrite, and galena as substrates. The results obtained with all three minerals show that hydrophobic force increases with increasing water contact angle, suggesting that hydrophobic forces are inherent properties of hydrophobic surfaces rather than created from artifacts such as preexisting nanobubbles and/or cavitation. A utility of the intrinsic relationship between hydrophobic force and contact angle is to predict flotation kinetics from the hydrophobicity of the minerals of interest. / Ph. D.

A study of the electrochemistry of the PbS-H₂O and PbS-KEX-H₂O systems has been made by carrying out thermodynamic calculations, electrochemical experiments and microflotation tests. Particular attention has been paid to how well this system can be described by equilibrium thermodynamics. The thermodynamic calculations are more comprehensive than previous ones of this type since they are based on a mass balance which includes both insoluble and soluble species. The data they provide include equilibrium concentrations of all dissolved species at any E_h and pH and an E_h-pH stability diagram for each collector addition. Also, two- and three-dimensional plots showing the effect of E_h and pH on xanthate uptake by the galena surface have been presented for the first time. These are particularly useful because they can be directly compared to observed flotation data. The results of voltammetry, IGP and potential-step experiments suggest that the oxidation of galena at pH 6.8 and 9.2 begins at a potential below the value predicted by bulk thermodynamics with the electrosorption of OH⁻ and the formation of a metal-deficient sulfide and a surface lead oxide. When oxidation becomes extensive enough, bulk products, Sº and PbO, begin to nucleate. Thiosulfate is detected at pH 9.2, but only becomes significant at high potentials. The electrochemical experiments indicate that xanthate adsorbs onto galena via a one-electron transfer chemisorption reaction in the first monolayer and via the formation of PbX₂ in subsequent layers. It also appears that galena oxidation and xanthate adsorption are competitive processes that tend to inhibit each other. Ground galena exhibits natural floatability at pH 9.2 as long as oxidation extends to the formation of a metal-deficient sulfide, but not to bulk PbO. When 10⁻⁵ M xanthate is added, the upper potential limit for flotation agrees well with the value predicted from thermodynamics for the decomposition of PbX₂. The lower limit, on the other hand, is at least 200 mv lower than any of the predicted values. PbS dissolves anodically at pH 1.1 and 4.6 to form Pb²⁺ and Sº first by a random surface process and then by a nucleation and growth mechanism once oxidation becomes extensive enough. At pH 0, the relation between the open-circuit potential and mineral solubility, as predicted by the thermodynamic calculations, agrees quantitatively with that determined experimentally. However, as the pH is increased to 1.1 and 4.6, the system becomes increasingly less reversible. / Ph. D.